JP2012224851A - Method for producing 2-cyanoethyl group-containing organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a 2-cyanoethyl group-containing organic compound having a high ratio of replacement by cyanoethyl groups and a high dielectric constant.SOLUTION: This invention relates to the method for producing a 2-cyanoethyl group-containing organic compound, comprising a step of reacting acrylonitrile with a hydroxyl group-containing organic compound through a Michael addition, wherein a quaternary ammonium salt is used as a catalyst.

Description

  The present invention is a method for producing a 2-cyanoethyl group-containing organic compound by a Michael addition reaction between acrylonitrile and a hydroxyl group-containing organic compound. By using a specific catalyst, the cyanoethyl group substitution rate is high and the dielectric constant is high. The present invention relates to a method for producing a 2-cyanoethyl group-containing organic compound.

  Since the 2-cyanoethyl group-containing organic compound contains a highly polar 2-cyanoethyl group, it forms a large dipole moment when placed in an electric field and exhibits a high dielectric constant. Or it is used in various fields that require a high dielectric material such as a heat-resistant separator for batteries.

Here, the 2-cyanoethyl group-containing organic compound can be produced, for example, by a Michael addition reaction between acrylonitrile and a hydroxyl group-containing organic compound.
So far, several methods have been proposed as a method for producing a 2-cyanoethyl group-containing organic compound by a Michael addition reaction between acrylonitrile and a hydroxyl group-containing organic compound (Patent Documents 1 to 4).

JP-A-56-18601 JP 59-22601 A JP-A-4-357695 JP-A-5-178903

In any of these methods, a basic substance such as caustic soda is used as a catalyst. Here, the catalyst has a function of increasing the nucleophilicity of the hydroxyl group of the hydroxyl group-containing organic compound and increasing the Michael addition reactivity with acrylonitrile. However, in the method using such a basic substance as a catalyst, there is a problem that the cyanoethylation substitution rate does not increase so much and the desired high dielectric property is not exhibited, and further, 2-cyanoethyl having a higher cyanoethylation substitution rate is present. There is a need for a method for producing a group-containing organic compound.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a 2-cyanoethyl group-containing organic compound having a high cyanoethylation substitution rate and a high dielectric constant.

  As a result of various studies to solve the above problems, the present inventors have found that a quaternary catalyst is used as a catalyst in a method for producing a 2-cyanoethyl group-containing organic compound by a Michael addition reaction between acrylonitrile and a hydroxyl group-containing organic compound. It has been found that by using an ammonium salt, a 2-cyanoethyl group-containing organic compound having a high cyanoethyl group substitution rate and a high dielectric constant can be produced, and the present invention has been completed.

  That is, the present invention is a method for producing a 2-cyanoethyl group-containing organic compound by a Michael addition reaction between acrylonitrile and a hydroxyl group-containing organic compound, characterized by using a quaternary ammonium salt as a catalyst. This is a method for producing a group-containing organic compound.

  ADVANTAGE OF THE INVENTION According to this invention, the 2-cyanoethyl group containing organic compound which has a high cyanoethylation substitution rate and a dielectric constant can be manufactured, and the performance of the application product using this can be improved.

The present invention will be described in detail below.
The 2-cyanoethyl group-containing organic compound can be produced by the following Michael addition reaction using a hydroxyl group-containing organic compound and acrylonitrile as starting materials.

R—OH + CH ₂ ═CH—CN → R—O—CH ₂ —CH ₂ —CN
(In the formula, R—OH represents a hydroxyl group-containing organic compound, and R—O—CH ₂ —CH ₂ —CN represents a 2-cyanoethyl group-containing organic compound.)

  The ratio of the number of moles of the hydroxyl group substituted with a cyanoethyl group to the number of moles of the hydroxyl group in the hydroxyl group-containing organic compound that is the starting material is called the cyanoethylation substitution rate (%).

  The hydroxyl group-containing organic compound is represented by R-OH, where R-OH is a monosaccharide such as glucose, fructose or galactose, a sugar such as a disaccharide such as maltose, sucrose or lactose, a sugar alcohol such as sorbitol or xylitol, cellulose, Polysaccharides such as starch and pullulan, alkylcelluloses such as methylcellulose and carboxymethylcellulose, hydroxyalkylcelluloses such as hydroxypropylcellulose, hydroxyethylcellulose and dihydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxypropylmethylcellulose and hydroxyethylmethylcellulose, dihydroxypropylpullulan Any of polysaccharide derivatives such as polyvinyl alcohol, polyvinyl alcohol, etc., or a combination thereof.

  Among these, polysaccharides, polysaccharide derivatives, or polyvinyl alcohol is particularly preferable in consideration of film-forming properties, binder properties, and the like for organic dispersion type EL applications and lithium ion secondary battery applications. This is because the 2-cyanoethyl group-containing organic compound that can be produced from these hydroxyl group-containing organic compounds is a polymer and therefore has excellent film-forming properties and binder properties.

  Examples of the quaternary ammonium salt include those represented by the following general formula (1) or (2).

R ¹ R ² R ³ R ⁴ N ⁺ .X ⁻ (1)
^{_{C 6 H 5 CH 2 R 5}} R 6 R 7 N + · X - (2)

^Wherein, R 1 to R ⁷ are the same or different 1 to 22 carbon atoms, preferably represents a straight-chain or branched aliphatic hydrocarbon group having 1 to 14 carbon atoms. Examples of such a linear aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group. Examples of the branched aliphatic hydrocarbon group include an isopropyl group and a 2-ethylhexyl group.

X ⁻ represents an anionic group and may be any one that forms a quaternary ammonium salt in combination with the quaternary ammonium ion, such as F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ COO ⁻ , CF ₃ SO ₄ ⁻ , CF ₃ CF ₂ SO ₄ ⁻ , SO ₄ ⁻ , OH ⁻ , CH ₃ SO ₄ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , HSO ₄ ⁻ , HF ₂ ⁻ , ICl ₄ ⁻ , BH _4- ^{and the} like.

  Specific examples of the quaternary ammonium ion in the general formula (1) include trimethylethylammonium, dimethyldiethylammonium, methyltriethylammonium, tetraethylammonium, trioctylmethylammonium, tetramethylammonium, tetra-n-butylammonium, trimethyldodecylammonium. , Trimethyltetradecyl ammonium, trimethylhexyl decyl ammonium, trimethyl octadecyl ammonium, trimethyl 2-ethylhexyl ammonium, dimethyl ethyl dodecyl ammonium, dimethyl ethyl tetradecyl ammonium, dimethyl ethyl hexadecyl ammonium, dimethyl ethyl octadecyl ammonium, dimethyl ethyl 2-ethylhexyl ammonium, Methyl diethyl Decyl ammonium, methyl diethyl tetradecyl ammonium, methyl diethyl hexadecyl ammonium, methyl diethyl ammonium methyl diethyl 2-ethylhexyl ammonium, dimethyl dihexyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl didodecyl ammonium, and the like.

  Specific examples of the quaternary ammonium ion in the general formula (2) include benzyltrimethylammonium, benzyltriethylammonium, benzyltri-n-butylammonium, benzyltetra-n-butylammonium, benzyldimethyldecylammonium, benzyldimethyldodecylammonium, benzyl Examples thereof include dimethyltetradecylammonium, benzyldimethylhexadecylammonium, benzyldimethyl 2-ethylhexylammonium and the like.

Examples of the quaternary ammonium salt represented by the general formula (1) or (2) include any combination of the quaternary ammonium ion and the anion X ⁻ . In the present invention, the quaternary ammonium salts represented by the general formula (1) or (2) may be used alone or in combination.

  Among these quaternary ammonium salts, considering the effect, price, availability, etc., either benzyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, or these Combinations are preferably used.

  The quaternary ammonium salt is added in an amount of 0.3 to 70 parts by mass, preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the hydroxyl group-containing organic compound. If the amount is less than 0.3 parts by mass, the substitution rate of cyanoethylation is low, and the desired high dielectric property may not be obtained. If the amount exceeds 70 parts by mass, the substitution rate of cyanoethylation does not improve, and the economic burden is met. There is no merit.

  In order to further improve the cyanoethylation substitution rate, a basic substance can be used in combination as a catalyst. Basic substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, Examples thereof include sodium hydrogen carbonate and the like, and alkali metal hydrogen carbonate of potassium hydrogen carbonate. These can be used alone or in combination of two or more.

  The basic substance is added in an amount of 0 to 70 parts by mass, preferably 0 to 50 parts by mass, with respect to 100 parts by mass of the hydroxyl group-containing organic compound. If the amount exceeds 70 parts by mass, the residual amount of metal impurities derived from the basic substance increases, which may deteriorate the performance of the applied product.

  When the quaternary ammonium salt is used alone and when the quaternary ammonium salt and the basic substance are used in combination, the content of the quaternary ammonium salt in the total mass of the catalyst is 0.5 to 100% by mass. The range, preferably 1.0 to 100% by mass is desirable. If the amount is less than 0.5% by mass, the cyanoethyl substitution rate is not improved, and the residual amount of metal salt impurities derived from the basic substance increases, which may deteriorate the performance of the applied product.

  As a specific example of the method for producing a 2-cyanoethyl group-containing organic compound, a hydroxyl group-containing organic compound is dissolved in water, then a quaternary ammonium salt or further basicity is added as a catalyst, and acrylonitrile is subsequently added. And it manufactures by performing reaction for 2 to 12 hours at 0-60 degreeC. In this case, the catalyst can be dissolved in water in advance, and then the hydroxyl group-containing organic compound can be dissolved therein, and then the reaction can be carried out by adding acrylonitrile. Acrylonitrile can also serve as a solvent, but if necessary, a diluting solvent that does not react with acrylonitrile, such as isopropyl alcohol, methyl ethyl ketone, and acetone, can also be added.

  The amount of acrylonitrile added depends on the cyanoethylation substitution rate of the 2-cyanoethyl group-containing organic compound as the reaction product, and is preferably in the range of 1 to 10 mol, more preferably 2 to 7 mol, per mol of hydroxyl group of the hydroxyl group-containing organic compound. And If the amount is less than 1 mole, the cyanoethyl substitution rate does not improve and the desired high dielectric properties may not be obtained. If the amount exceeds 10 moles, the cyanoethyl substitution rate is not improved, which is suitable for the economic burden. There is no merit. When acrylonitrile also serves as a solvent, the amount of acrylonitrile added is 3 mol or more, preferably 6 mol or more, per mol of hydroxyl group of the hydroxyl group-containing organic compound. If the amount is less than 3 mol, the viscosity of the reaction solution increases, and the reaction solution may not be sufficiently stirred. The cyanoethylation substitution rate of the 2-cyanoethyl group-containing organic compound can be measured from the nitrogen content determined by the Kjeldahl method.

  After completion of the reaction, the organic layer is taken out and water is added thereto to precipitate the product. Although the precipitated crude product is purified by washing with a large amount of water, the product may be purified by dissolving it in a solvent such as acetone or methyl ethyl ketone and reprecipitating it. After purification, dehydration and drying are finally performed to obtain a 2-cyanoethyl group-containing organic compound.

  The characteristics of the 2-cyanoethyl group-containing organic compound produced in this way are that the cyanoethylation substitution rate and dielectric constant are high, and there are few metal salt impurities. In the case of an organic dispersion type EL of a light emitting element used as a liquid crystal display of a mobile terminal device or as a backlight for road signs and advertisements, the higher the dielectric constant of the binder used, the higher the brightness and the metal salt impurities contained. The smaller the amount, the longer the life of the EL. Therefore, by using the 2-cyanoethyl group-containing organic compound produced by the production method of the present invention, the brightness and life of the organic dispersion type EL are improved, and the quality of the applied product is improved. Can be increased. Further, it is well known that a substance having a high dielectric constant has good ionic conductivity. Since a material having high ion conductivity is useful for improving the performance such as load characteristics of a lithium ion battery, it can be expected to be applied in this field. For example, a heat-resistant separator used in a lithium ion battery has a heat-resistant porous layer in which inorganic particles such as alumina are hardened with a binder on one or both sides of a separator substrate such as a polyolefin-based film, and has improved heat resistance. It is a separator. If a 2-cyanoethyl group-containing organic compound having excellent ion conductivity is used as a binder for this separator, a lithium ion battery having a heat-resistant separator with a heat-resistant porous layer will have excellent load characteristics. . Moreover, since the 2-cyanoethyl group-containing organic compound has few metal salt impurities as described above, it can provide a lithium ion battery with good cycle characteristics.

  Hereinafter, although the specific aspect of this invention is demonstrated based on an Example and a comparative example, this invention is not restrict | limited to the following Example.

[Example 1]
After adding 4.55 parts by mass of water to a reaction flask equipped with a stirrer and dissolving 1 part by mass of pullulan, 0.75 parts by mass of 40% by mass benzyltrimethylammonium hydroxide aqueous solution (converted to benzyltrimethylammonium hydroxide: 0.3) Part by mass), 5 parts by mass of acrylonitrile and 4 parts by mass of acetone were added thereto, and the mixture was reacted at 25 ° C. for 8 hours.
Then, 20 mass% acetic acid aqueous solution containing acetic acid equivalent to benzyltrimethylammonium hydroxide was added. The reaction solution was divided into two layers, an aqueous layer and an organic layer. The organic layer was extracted and stirred while being poured into water to precipitate crude 2-cyanoethyl pullulan.
Crude 2-cyanoethyl pullulan was washed repeatedly with water, redissolved in acetone, precipitated again in water, dehydrated and dried under reduced pressure to obtain purified 2-cyanoethyl pullulan.

[Example 2]
After adding 7.55 parts by mass of water to a reaction flask equipped with a stirrer and dissolving 1 part by mass of polyvinyl alcohol (PVA), 0.75 parts by mass of a 40% by mass benzyltrimethylammonium hydroxide aqueous solution (as converted to benzyltrimethylammonium hydroxide) : 0.3 parts by mass), and 6.5 parts by mass of acrylonitrile and 4.5 parts by mass of acetone were added thereto and reacted at 32 ° C. for 6 hours. Polyvinyl alcohol was obtained.

[Example 3]
After charging 4.85 parts by mass of water in a reaction flask equipped with a stirrer and dissolving 1 part by mass of pullulan, 0.25 part by mass of 40% by mass benzyltrimethylammonium hydroxide aqueous solution (converted to benzyltrimethylammonium hydroxide: 0.1) 2-Cyanoethyl pullulan was obtained in the same manner as in Example 1 except that (part by mass) was added.

[Example 4]
2-Cyanoethyl pullulan was obtained in the same manner as in Example 1 except that the amount of acrylonitrile added was 2 parts by mass and the reaction was carried out at 15 ° C. for 20 hours.

[Example 5]
After charging 8 parts by mass of water in a reaction flask equipped with a stirrer and dissolving 1 part by mass of hydroxyethyl cellulose (HEC) having a substitution mole number of 1.5, 0.75 part by mass of a 40% by mass benzyltrimethylammonium hydroxide aqueous solution was added, To this, 4.0 parts by mass of acrylonitrile and 4.5 parts by mass of acetone were added, and the mixture was inverted at 32 ° C. for 6 hours. The reaction solution was divided into two layers, an aqueous layer and an organic layer. The organic layer was extracted and stirred while being poured into water to precipitate crude 2-cyanoethylhydroxyethyl cellulose. The crude 2-cyanoethylhydroxyethylcellulose was repeatedly washed with water, redissolved in acetone, precipitated again in water, dehydrated and dried under reduced pressure to obtain purified cyanoethylhydroxypropylcellulose.

[Example 6]
After charging 7.3 parts by mass of water in a reaction flask equipped with a stirrer and dissolving 1 part by mass of polyvinyl alcohol (PVA), 0.2 part by mass of benzyltriethylammonium chloride and 0.7 parts by mass of a 10% by mass aqueous caustic soda solution (caustic soda (Equivalent amount: 0.07 parts by mass) was added, and 6.5 parts by mass of acrylonitrile and 4.5 parts by mass of acetone were added and reacted at 32 ° C. for 6 hours, and then 20% by mass containing acetic acid equivalent to caustic soda. Of acetic acid in water was added. Thereafter, the same treatment as in Example 1 was carried out to obtain 2-cyanoethyl polyvinyl alcohol.

[Example 7]
After charging 4.4 parts by weight of water into a reaction flask equipped with a stirrer and dissolving 1 part by weight of polyvinyl alcohol, 0.0125 parts by weight of benzyltriethylammonium chloride and 10% by weight aqueous caustic soda solution (caustic soda equivalent: 0.4 parts by weight) ) And 6.5 parts by weight of acrylonitrile and 4.5 parts by weight of acetone were added thereto and reacted at 32 ° C. for 6 hours. Thereafter, the same treatment as in Example 6 was carried out to obtain 2-cyanoethyl polyvinyl alcohol.

[Comparative Example 1]
After charging 2.3 parts by weight of water into a reaction flask equipped with a stirrer and dissolving 1 part by weight of pullulan, 5.5 parts by weight of 10% by weight aqueous caustic soda solution (caustic soda equivalent: 0.55 parts by weight) was added thereto. 5 parts by mass of acrylonitrile and 4 parts by mass of acetone were added and reacted at 25 ° C. for 8 hours, and then a 20% by mass acetic acid aqueous solution containing acetic acid equivalent to caustic soda was added. Thereafter, the same treatment as in Example 1 was carried out to obtain 2-cyanoethyl pullulan.

[Comparative Example 2]
After 4.4 parts by weight of water was charged into a reaction flask equipped with a stirrer and 1 part by weight of polyvinyl alcohol was dissolved, 5.5 parts by weight of 10% by weight aqueous caustic soda solution (caustic soda equivalent: 0.55 parts by weight) was added. To the mixture, 6.5 parts by mass of acrylonitrile and 4.5 parts by mass of acetone were added and reacted at 32 ° C. for 6 hours. Thereafter, the same treatment as in Example 6 was carried out to obtain 2-cyanoethyl polyvinyl alcohol.

The nitrogen content of the 2-cyanoethyl pullulan, 2-cyanoethyl polyvinyl alcohol, and 2-cyanoethyl hydroxyethyl cellulose (hereinafter sometimes referred to as “sample”) obtained in Examples and Comparative Examples is determined by the Kjeldahl method. From this analytical value, the cyanoethylation substitution rate was determined.
Further, the nitrogen content of the obtained sample, the relative dielectric constant, and the ash content as an index of the metal salt impurity contained in the sample were measured by the following method. These results are shown in Table 1.

Measurement of Nitrogen Content A sample was accurately weighed into a Kjeldahl flask, sulfuric acid was added, and potassium sulfate for increasing the boiling point of the liquid and copper sulfate as a catalyst for promoting decomposition were added and stirred well. The flask was heated until the solution boiled, and the reaction was allowed to proceed. When the liquid became transparent, the heating was stopped and the mixture was allowed to stand until it reached room temperature. Sodium hydroxide and water were added to make it alkaline and distilled. The distillate was introduced into an aqueous hydrochloric acid solution having a known concentration to absorb the ammonia contained therein. By adding a pH indicator to this aqueous solution and performing titration, the nitrogen content contained in the sample was calculated.

Ash content was measured by the following method using ash content as an indicator of the amount of residual metal salt impurities.
5 parts by mass of a sample is accurately placed in a magnetic crucible, heated on a hot plate and carbonized. After cooling, add 1 part by volume of concentrated sulfuric acid and heat until no white smoke of sulfuric acid is produced.
Next, this is heated to a constant weight in an electric furnace at 450 to 550 ° C., allowed to cool, and then the remaining amount is measured. Ash content (mass%) is calculated from the following equation.

    Ash content (sulfate)% = {remaining amount (g) / sample (g)} × 100

Measurement of dielectric constant A sample is dissolved in a mixed solvent of acetone / dimethylformamide (9/1 mass ratio), cast on an aluminum foil, and dried at 120 ° C. for 4 hours to prepare a film having a thickness of about 40 μm.
Next, aluminum was vapor-deposited on the surface, and the capacitance was obtained by a method of measuring capacitance with an LCR meter under the conditions of 1 V, 1 KHz, 20 ° C. and alternating current.

Examples 1 to 5 using a quaternary ammonium salt as a catalyst, and Examples 6 and 7 using a quaternary ammonium salt and a basic substance in combination have a higher cyanoethyl group substitution rate, compared with the comparative example. It is clear that the dielectric constant has increased. In Examples 1 to 7, the basic substance was not used or the amount used was small, resulting in a small amount of ash as an indicator of the amount of residual metal salt impurities.
On the other hand, in Comparative Examples 1 and 2 using only a basic substance as a catalyst, the cyanoethyl group substitution rate was low and the dielectric constant was low as compared with the Examples. Moreover, since the usage-amount of the basic substance was much, the result also had much ash content.

  Further, Table 2 shows the results of evaluation as an organic dispersion type EL and evaluation as a lithium ion secondary battery according to the following method.

2 parts by mass of N, N′-dimethylformamide was added to 1 part by mass of an evaluation sample as an organic dispersion type EL , and the mixture was stirred and dissolved at room temperature. This sample solution is blended with 3.2 parts by mass of electroluminescent zinc sulfide phosphor for EL having an average particle size of 28 μm (type 723L, manufactured by Sylvania USA, ZnS: Cu), kneaded well, and used for the light emitting layer. A phosphor paste was prepared. Further, 4.6 parts by mass of barium titanate (BT-100P, manufactured by Fuji Titanium Co., Ltd.) having an average particle diameter of 1.5 μm was blended with 3 parts by mass of the sample solution having the same composition, and kneaded well. A paste was prepared.
Next, the insulating reflective layer paste is printed on an 80 μm thick aluminum sheet substrate by a screen printing method, and after drying, the phosphor paste is applied onto the layer by the same screen printing method and dried. A light emitting layer was formed. The thickness of the layer after drying was about 24 μm for the insulating reflective layer and about 65 μm for the light emitting layer.
Next, after the silver paste is printed and dried as a power supply line on the conductive surface side of the transparent conductive film (Electrista 300C, manufactured by Nitto Denko Corporation), and the lead electrode made of phosphor bronze is attached, the power supply printed surface of the transparent conductive film And the light emitting layer were overlaid and heat-pressed (140 ° C., 5 kg / cm ² ). After attaching the lead electrode to the aluminum sheet substrate to be the back electrode, a moisture-proof sheet made of polychlorotrifluoroethylene (EL sealer No. 4810N, the same as above) is thermocompression-bonded (120 ° C., 5 kg) to the entire laminated element. / cm ² ) to obtain an organic dispersion type EL. The initial luminance when a voltage of 1 KHz and 100 V was applied to these elements and the half-life (time during which the luminance becomes half of the initial luminance) when left in an atmosphere at a temperature of 50 ° C. and a humidity of 90% were measured.

Evaluation as a lithium ion secondary battery
[Manufacture of separators]
40 parts by mass of Al ₂ O ₃ (alumina) was added to a solution obtained by dissolving 10 parts by mass of a sample in 190 parts by mass of methyl ethyl ketone, and mixed with a ball mill to prepare a slurry. The prepared slurry was coated on a polyethylene microporous film (thickness 16 μm, porosity 40%) by dip coating, and dried to prepare a heat-resistant separator.

[Manufacture of positive electrode]
85 parts by mass of LiCoO ₂ that is a positive electrode active material, 10 parts by mass of acetylene black that is a conductive auxiliary agent, and 5 parts by mass of PVDF that is a binder are made uniform using N-methyl-2-pyrrolidone (NMP) as a solvent. To prepare a positive electrode mixture-containing paste. This positive electrode mixture-containing paste was applied to both sides of a current collector made of aluminum foil and having a thickness of 15 μm, dried, and then calendered to produce a positive electrode having a total thickness of 150 μm. Further, a tab was welded to the exposed portion of the aluminum foil of the positive electrode to form a lead portion.

[Manufacture of negative electrode]
A negative electrode mixture-containing paste was prepared by mixing 95 parts by mass of graphite as a negative electrode active material and 5 parts by mass of PVDF as a binder so as to be uniform using NMP as a solvent. This negative electrode mixture-containing paste was applied to both sides of a 10 μm thick current collector made of copper foil, dried, and then calendered to produce a negative electrode having a total thickness of 142 μm. Further, a tab was welded to the exposed portion of the copper foil of the negative electrode to form a lead portion.

<Manufacture of batteries>
The positive electrode and the negative electrode obtained by the method described above were spirally wound through the following separator to form a wound electrode body. The wound electrode body is crushed into a flat shape, placed in an aluminum outer can, and an organic electrolyte (a mixture of ethylene carbonate and ethyl methyl carbonate in a volume ratio of 2: 1, LiPF ₆ at a concentration of 1 mol / l). After injecting the dissolved solution, sealing was performed to prepare a lithium ion secondary battery.

<Evaluation of battery cycle characteristics>
About the produced lithium ion secondary battery, charging / discharging was repeated 100 cycles using the charging / discharging measuring apparatus (HJ-101SM6 by Hokuto Denko KK). As charging / discharging conditions, charging was performed up to 4.2 V at 1.6 mA / h, and discharging was performed up to 2.75 V at 1.6 mA / h.
The cycle characteristics were calculated from the discharge capacity at the first cycle and the discharge capacity at the 100th cycle as follows. When the cycle characteristic was 80% or more, it was evaluated as good (◯), and when it was less than 80%, it was judged as defective (×).

  Cycle characteristics (%) = (discharge capacity at the 100th cycle) ÷ (discharge capacity at the first cycle) × 100

<Evaluation of load characteristics>
The prepared lithium ion secondary battery is charged with constant current at a current value of 0.2 C until the battery voltage reaches 4.2 V, and then, constant current-constant voltage charging is performed with constant voltage charging at 4.2 V. went. The total charging time until the end of charging was 15 hours. Each battery after charging was discharged at a discharge current of 0.2 C until the battery voltage reached 3.0 V, and the discharge capacity (0.2 C discharge capacity) was measured. Next, after charging each battery under the same conditions as described above, the battery was discharged at a discharge current of 2C until the battery voltage reached 3.0 V, and the discharge capacity (2C discharge capacity) was measured. The ratio (load characteristic) of 2C discharge capacity to 0.2C discharge capacity was examined. In addition, all the said charge and discharge were implemented in the environment whose temperature is 20 degreeC.

The organic dispersion type EL using the 2-cyanoethyl group-containing organic compounds of Examples 1 to 7 has high initial luminance due to the high dielectric constant due to the influence of a high cyanoethyl group substitution rate, and contains metal salt impurities. Due to the small amount, the half-life was also long.
On the other hand, the organic dispersion type EL using the 2-cyanoethyl group-containing organic compound of Comparative Example 1 and Comparative Example 2 did not have a high dielectric constant due to the influence of a low cyanoethyl group substitution rate, so that the initial luminance did not increase. In addition, since the content of metal salt impurities is large due to a large amount of ash, the organic dispersion type EL has a short half-life and a short life.

The lithium ion secondary batteries using the 2-cyanoethyl group-containing organic compounds of Examples 1 to 7 have excellent cycle characteristics due to the small amount of metal salt impurities. Moreover, since the ionic conductivity was excellent due to the high dielectric constant, the load characteristics were also excellent.
On the other hand, since the lithium ion secondary battery using the cyanoethyl group-containing organic compound of Comparative Examples 1 and 2 has a high ash content and a high content of metal salt impurities, a 2-cyanoethyl group-containing machine compound is used. The cycle characteristics were poor. Moreover, since the dielectric constant was low and the ionic conductivity was not good, a lithium ion secondary battery with poor load characteristics was obtained.

  From the above results, the use of a quaternary ammonium salt as a catalyst in producing a 2-cyanoethyl group-containing organic compound improves the brightness and life of the organic EL, and the cycle characteristics and additional characteristics of the lithium ion secondary battery. It is clear that this will result.

  According to the production method of the present invention, a 2-cyanoethyl group-containing organic compound having a high cyanoethylation substitution rate and a high dielectric constant can be easily produced.

Claims (5)

A method for producing a 2-cyanoethyl group-containing organic compound by a Michael addition reaction between acrylonitrile and a hydroxyl group-containing organic compound,
A method for producing a 2-cyanoethyl group-containing organic compound, wherein a quaternary ammonium salt is used as a catalyst.   2. The 2-cyanoethyl group-containing organic material according to claim 1, wherein the quaternary ammonium salt is benzyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, or a combination thereof. Compound production method.   The method for producing a 2-cyanoethyl group-containing organic compound according to claim 1 or 2, wherein a basic substance is further used in combination as the catalyst.   The 2-cyanoethyl group-containing composition according to claim 3, wherein the basic substance is any one of an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, or a combination thereof. A method for producing an organic compound.   The 2-cyanoethyl group-containing organic compound according to any one of claims 1 to 4, wherein the hydroxyl group-containing organic compound is any one of saccharides, sugar alcohols, polysaccharides, polysaccharide derivatives and polyvinyl alcohol, or a combination thereof. Manufacturing method.